EP0780371A2 - Esters d'acide 2-alkylmercapto-4-trifluorométhyl-benzoique ainsi qu'un procédé pour leur préparation - Google Patents
Esters d'acide 2-alkylmercapto-4-trifluorométhyl-benzoique ainsi qu'un procédé pour leur préparation Download PDFInfo
- Publication number
- EP0780371A2 EP0780371A2 EP96119753A EP96119753A EP0780371A2 EP 0780371 A2 EP0780371 A2 EP 0780371A2 EP 96119753 A EP96119753 A EP 96119753A EP 96119753 A EP96119753 A EP 96119753A EP 0780371 A2 EP0780371 A2 EP 0780371A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- trifluoromethyl
- alkyl
- formula
- benzoic acid
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- -1 alkyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- XILPLWOGHPSJBK-UHFFFAOYSA-N 1,2-dichloro-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Cl)C(Cl)=C1 XILPLWOGHPSJBK-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002168 alkylating agent Substances 0.000 claims description 2
- 229940100198 alkylating agent Drugs 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 150000008050 dialkyl sulfates Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- UDXPRKSPAZWHQN-UHFFFAOYSA-N 3-chloro-4-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(C(F)(F)F)C(Cl)=C1 UDXPRKSPAZWHQN-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 239000000010 aprotic solvent Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000003408 phase transfer catalysis Methods 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- DTIJZEUKFYGSEC-UHFFFAOYSA-N 2-chloro-4-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(C(F)(F)F)C=C1Cl DTIJZEUKFYGSEC-UHFFFAOYSA-N 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- BJYHBJUWZMHGGQ-UHFFFAOYSA-N 1,2-dichloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(Cl)=C1Cl BJYHBJUWZMHGGQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- YEJXRKIOCTUZFG-UHFFFAOYSA-N ethyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound CCOC(=O)C1=CC=C(C(F)(F)F)C=C1Cl YEJXRKIOCTUZFG-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GJPRWVJTMJTVMN-UHFFFAOYSA-N butyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound CCCCOC(=O)C1=CC=C(C(F)(F)F)C=C1Cl GJPRWVJTMJTVMN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- QJZUPDUXEBVQHR-UHFFFAOYSA-N methyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC=C(C(F)(F)F)C=C1Cl QJZUPDUXEBVQHR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- QYRNHUQEODSVDD-UHFFFAOYSA-N 2-methylpropyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound CC(C)COC(=O)C1=CC=C(C(F)(F)F)C=C1Cl QYRNHUQEODSVDD-UHFFFAOYSA-N 0.000 description 1
- OIPVMXHTTCOSJX-UHFFFAOYSA-N 3-methylbutyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=C(C(F)(F)F)C=C1Cl OIPVMXHTTCOSJX-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XSIFPSYPOVKYCO-UHFFFAOYSA-N benzoic acid butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N benzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VYCRKIAQVKMADW-UHFFFAOYSA-N butan-2-yl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound CC(CC)OC(C1=C(C=C(C=C1)C(F)(F)F)Cl)=O VYCRKIAQVKMADW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MFONLERCLOWQGK-UHFFFAOYSA-N methyl 2-methyl-3-sulfanyl-4-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC=C(C(F)(F)F)C(S)=C1C MFONLERCLOWQGK-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- CMEZUWJPYFHWGJ-UHFFFAOYSA-N pentyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound CCCCCOC(=O)C1=CC=C(C(F)(F)F)C=C1Cl CMEZUWJPYFHWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- ZGLTXPXDRUPGEU-UHFFFAOYSA-N propyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound CCCOC(=O)C1=CC=C(C(F)(F)F)C=C1Cl ZGLTXPXDRUPGEU-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Definitions
- the present invention relates to new 2-alkylmerkapto-4- (trifluoromethyl) benzoic acid esters and a process for their preparation.
- 2-alkylmerkapto-4- (trifluoromethyl) benzoic acid esters are valuable intermediates for the preparation of a herbicide which is used in maize crops (see EP 527036, EP 470 856).
- EP 524 018 (Reference Examples 17 and 18) and EP 527 036 (Reference Example 6) describe the preparation of 2-methylmerkapto-4-trifluoromethylbenzoic acid in the following way.
- a disadvantage of this method is the difficult to access starting material and the use of organometallic reagents, which lead to safety-related problems when transferred on a larger scale.
- the first step in the synthesis of 2-alkylmerkapto-4- (trifluoromethyl) benzoic esters involves the electrochemical reductive carboxylation of 3,4-dichlorobenzotrifluoride to magnesium 2-chloro-4- (trifluoromethyl) benzoate.
- An undivided electrolysis cell which can be of any shape, is expediently used, for example a trough-shaped cell or a flow-through cell which has at least one cathode and one anode.
- the cathode consists of one of the usual metals, for example aluminum, magnesium, iron, nickel, chromium, titanium, copper, lead, zinc, tin, cadmium, silver, gold or platinum as well as alloys of these metals or of carbon materials, for example graphite or vitreous carbon .
- Lead, cadmium and tin are preferably used.
- Metals which are difficult to deposit cathodically under the electrolysis conditions for example aluminum, calcium or preferably magnesium, are used as the anode.
- Aprotic dipolar solvents are suitable as electrolytes, for example acetonitrile, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran or preferably dimethylformamide.
- Indifferent salts which are soluble in the electrolyte preferably tetraalkylammonium salts, are used as conductive salts.
- the electrolyte is saturated with CO 2 . This can be ensured by continuously passing a CO 2 stream or by working in a pressure cell.
- the electrolysis is carried out at temperatures between approximately 0 ° C. and 80 ° C., preferably between 0 ° C. and 20 ° C.
- the electrolysis takes place at current densities between approximately 1 and 100 mA / cm 2 , preferably between 5 and 50 mA / cm 2 .
- it is convenient to stir or flow the Electrolyte moves relative to the electrodes.
- the second step of the manufacturing process involves the esterification of the electrochemically produced 2-chloro-4- (trifluoromethyl) benzoate to 2-chloro-4- (trifluoromethyl) benzoic acid esters.
- the esterification is preferably carried out without prior purification of the crude electrolyte in such a way that the concentrated crude electrolyte is reacted with the alcohol to be esterified and a strong column and heated under reflux.
- the esterification can also be carried out in a 2-phase system consisting of water and an immiscible organic solvent using strong alkylating agents, for example dialkyl sulfates. Tetralkylammonium salts, for example tetrabutylammonium hydrogen sulfate, are used here as phase transfer catalysts.
- the pH is kept at 7 by adding base or by using buffer systems.
- Products of formula (I) are e.g. Methyl 2-chloro-4- (trifluoromethyl) benzoate, ethyl 2-chloro-4- (trifluoromethyl) benzoate, propyl 2-chloro-4- (trifluoromethyl) benzoate, 2-chloro-4- (trifluoromethyl) ) -benzoic acid-isopropyl ester, 2-chloro-4- (trifluoromethyl) -benzoic acid-1-butyl ester, 2-chloro-4- (trifluoromethyl) -benzoic acid-2-butyl ester, 2-chloro-4- (trifluoromethyl) -benzoic acid- isobutyl ester, 2-chloro-4- (trifluoromethyl) benzoic acid t-butyl ester, 2-chloro-4- (trifluoromethyl) benzoic acid amyl ester, 2-chloro-4- (trifluoromethyl) benzoic acid is
- the 2-alkylmerkapto-4- (trifluoromethyl) benzoic acid esters are prepared according to the invention by reacting one of the 2-chloro-4- (trifluoromethyl) benzoic acid esters listed above with an alkali metal, alkaline earth metal or Ammonium alkyl mercaptide in an org. Solvents from the group of alcohols, ethers, hydrocarbons, aromatics or another dipolar solvent such as DMF. The alkyl mercaptide can also be generated in situ by using the free alkyl mercaptan in the presence of an inorganic or organic base such as soda or a tertiary amine.
- the reaction with the alkyl mercaptide is carried out at temperatures from 0 ° C to 150 ° C.
- the process products are isolated, for example, by evaporating the solvent and isolating the crude product obtained as a residue by fractional distillation or crystallization.
- the invention further relates to compounds of the formula (I) in which R 1 is (C 1 -C 6 ) alkyl and compounds of the formula (II) in which R 1 and R 2 (C 1 -C 6 ) are alkyl, in particular compounds of the formula (II) with R 1 equal to ethyl and R 2 equal to methyl and compounds of formula (I) with R 1 equal to ethyl.
- the reductive carboxylation of 3,4-dichlorobenzotrifluoride is carried out electrochemically in an undivided electrolysis cell.
- the cell consists of a cylindrical glass vessel with a cooling jacket and a ground glass lid, in which there are 3 smaller cut openings.
- a magnesium plate (length: 110 mm; width: 55 mm; immersion depth: 100 mm) is used as the anode; a cadmium plate with the same dimensions is used as the cathode.
- the electrodes are held in the lid of the cell by rigid platinum wire that serves as a power supply.
- the cell is also equipped with a gas inlet tube for carbon dioxide combined with a bubble counter.
- the electrolyte is stirred with a magnetic rod.
- the dry cell is charged with 350 DMF, 21.5 g 3,4-dichlorobenzotrifluoride and 2.7 g tetrabutylammonium bromide.
- a constant stream of CO 2 is passed through the electrolyte with stirring in order to ensure a solution saturated with CO 2 , and after 1/2 hour the electrolysis is started with continued stirring and passing through a weak CO 2 stream.
- the current is constant 1.1 A, the temperature 15 ° C.
- the cell voltage is initially in the range of 3 to 9 V and increases towards approx. 25 V towards the end.
- the amount of charge is 2 F / mol.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nonwoven Fabrics (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19548428A DE19548428C1 (de) | 1995-12-22 | 1995-12-22 | 2-Alkylmerkapto-4-(trifluormethyl)-benzoesäureester sowie ein Verfahren zu ihrer Herstellung |
| DE19548428 | 1995-12-22 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0780371A2 true EP0780371A2 (fr) | 1997-06-25 |
| EP0780371A3 EP0780371A3 (fr) | 1998-04-29 |
| EP0780371B1 EP0780371B1 (fr) | 2000-08-23 |
Family
ID=7781207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96119753A Expired - Lifetime EP0780371B1 (fr) | 1995-12-22 | 1996-12-10 | Esters d'acide 2-alkylmercapto-4-trifluorométhyl-benzoique ainsi qu'un procédé pour leur préparation |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5744021A (fr) |
| EP (1) | EP0780371B1 (fr) |
| JP (1) | JPH09286774A (fr) |
| CN (1) | CN1070946C (fr) |
| CA (1) | CA2193608A1 (fr) |
| DE (2) | DE19548428C1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002489A1 (fr) * | 1997-07-07 | 1999-01-21 | Rhone Poulenc Agro | Procede de preparation de derives de l'acide 2-alkylthio benzoique |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398492C (zh) * | 2005-08-01 | 2008-07-02 | 中国人民解放军国防科学技术大学 | 一种气凝胶绝热复合材料及其制备方法 |
| CN101985422A (zh) * | 2010-10-25 | 2011-03-16 | 华东师范大学 | 一种对乙酰基苯甲酸甲酯的合成方法 |
| CN104789986B (zh) * | 2015-04-30 | 2017-08-25 | 湖南海利常德农药化工有限公司 | 2‑氯‑4‑三氟甲基苯甲酸的制备方法 |
| CN104926702A (zh) * | 2015-04-30 | 2015-09-23 | 湖南海利化工股份有限公司 | 2-甲硫基-4-三氟甲基苯甲酸甲酯的制备方法 |
| TWI721034B (zh) * | 2015-11-30 | 2021-03-11 | 德商拜耳作物科學公司 | 藉由化學選擇性硫醚氧化製備2-烷基-4-三氟甲基-3-烷基磺醯基苯甲酸之方法 |
| JP6634595B2 (ja) | 2016-02-18 | 2020-01-22 | パナソニックＩｐマネジメント株式会社 | 断熱材及びその製造方法 |
| CN107099692A (zh) * | 2016-02-20 | 2017-08-29 | 金承黎 | 一种纤维增强气凝胶-金属复合材料及其制备方法 |
| CN105862157A (zh) * | 2016-06-12 | 2016-08-17 | 李光武 | 一种隔热保温纤维材料及其制备方法、用途 |
| CN106245054A (zh) * | 2016-09-05 | 2016-12-21 | 聊城大学 | 一种2‑氯苯甲酸甲酯的合成方法 |
| CN107354477A (zh) * | 2017-07-08 | 2017-11-17 | 聊城大学 | 一种异烟酸的合成方法 |
| CN107324996A (zh) * | 2017-07-08 | 2017-11-07 | 聊城大学 | 一种对氯苯甲酸甲酯的合成方法 |
| CN107400898A (zh) * | 2017-07-22 | 2017-11-28 | 聊城大学 | 一种2‑吡啶甲酸甲酯的合成方法 |
| JP7029589B2 (ja) * | 2017-12-08 | 2022-03-04 | パナソニックＩｐマネジメント株式会社 | 断熱材 |
| WO2021000927A1 (fr) * | 2019-07-03 | 2021-01-07 | 东丽纤维研究所（中国）有限公司 | Matériau thermo-isolant et ignifuge et son application |
| CN111690947B (zh) * | 2020-06-17 | 2021-10-15 | 浙江工业大学 | 三氟甲基化芳基酰胺衍生物的电化学合成方法 |
| CN113578286B (zh) * | 2021-08-23 | 2023-04-28 | 衢州学院 | 吸附材料及其制备方法和应用 |
| CN116925547B (zh) * | 2023-08-25 | 2024-03-15 | 江西聚真科技发展有限公司 | 一种低摩擦系数聚苯硫醚材料及其制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0470856A1 (fr) | 1990-08-10 | 1992-02-12 | Rhone-Poulenc Agriculture Ltd. | Dérivés d'isoxazole, procédés pour leur fabrication et leurs applications comme herbicides |
| EP0524018A1 (fr) | 1991-07-17 | 1993-01-20 | Rhone-Poulenc Agriculture Ltd. | Isoxazoles herbicides |
| EP0527036A1 (fr) | 1991-08-05 | 1993-02-10 | Rhone-Poulenc Agriculture Ltd. | Dérivés de 4-benzoylisoxazole et leur utilisation comme herbicides |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855285A (en) * | 1971-06-21 | 1974-12-17 | Pfizer | Acylmethylthio-trifluoromethyl-benzoic acids |
| US3867407A (en) * | 1971-08-23 | 1975-02-18 | Jurg R Pfister | Substituted xanthone carboxylic acid compounds |
| IL74694A0 (en) * | 1984-04-02 | 1985-06-30 | Merck & Co Inc | N-alkenyl-3-hydroxybenzo(b)thiophene-2-carboxamide derivatives,their preparation and pharmaceutical compositions containing them |
| US4692545A (en) * | 1986-12-12 | 1987-09-08 | Stauffer Chemical Company | Method for preparation of mercaptobenzoates |
| US4704467A (en) * | 1986-12-12 | 1987-11-03 | Stauffer Chemical Company | Method for preparation of mercaptobenzoates |
| EP0365483B1 (fr) * | 1988-10-20 | 1993-12-29 | Ciba-Geigy Ag | Esters d'acide mercaptobenzoique utilisés comme stabilisateurs de polymérisats contenant du chlore |
| EP0432438B1 (fr) * | 1989-11-02 | 1994-02-02 | Kuraray Chemical Co., Ltd. | Adsorbant moulé |
| US5565142A (en) * | 1992-04-01 | 1996-10-15 | Deshpande; Ravindra | Preparation of high porosity xerogels by chemical surface modification. |
-
1995
- 1995-12-22 DE DE19548428A patent/DE19548428C1/de not_active Expired - Fee Related
-
1996
- 1996-12-10 EP EP96119753A patent/EP0780371B1/fr not_active Expired - Lifetime
- 1996-12-10 DE DE59605791T patent/DE59605791D1/de not_active Expired - Fee Related
- 1996-12-19 JP JP8340031A patent/JPH09286774A/ja not_active Withdrawn
- 1996-12-20 CN CN96199193A patent/CN1070946C/zh not_active Expired - Fee Related
- 1996-12-20 US US08/770,325 patent/US5744021A/en not_active Expired - Lifetime
- 1996-12-20 CA CA002193608A patent/CA2193608A1/fr not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0470856A1 (fr) | 1990-08-10 | 1992-02-12 | Rhone-Poulenc Agriculture Ltd. | Dérivés d'isoxazole, procédés pour leur fabrication et leurs applications comme herbicides |
| EP0524018A1 (fr) | 1991-07-17 | 1993-01-20 | Rhone-Poulenc Agriculture Ltd. | Isoxazoles herbicides |
| EP0527036A1 (fr) | 1991-08-05 | 1993-02-10 | Rhone-Poulenc Agriculture Ltd. | Dérivés de 4-benzoylisoxazole et leur utilisation comme herbicides |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002489A1 (fr) * | 1997-07-07 | 1999-01-21 | Rhone Poulenc Agro | Procede de preparation de derives de l'acide 2-alkylthio benzoique |
| US6777575B2 (en) | 1997-07-07 | 2004-08-17 | Rhone-Poulenc Agro | Process for the preparation of 2-alkylthio benzoic acid derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09286774A (ja) | 1997-11-04 |
| CN1070946C (zh) | 2001-09-12 |
| CN1205751A (zh) | 1999-01-20 |
| DE59605791D1 (de) | 2000-09-28 |
| EP0780371B1 (fr) | 2000-08-23 |
| DE19548428C1 (de) | 1997-08-28 |
| US5744021A (en) | 1998-04-28 |
| CA2193608A1 (fr) | 1997-06-23 |
| EP0780371A3 (fr) | 1998-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0780371B1 (fr) | Esters d'acide 2-alkylmercapto-4-trifluorométhyl-benzoique ainsi qu'un procédé pour leur préparation | |
| EP0011712B1 (fr) | La préparation de dialcoylacétals de benzaldéhyd substitués en position 4 | |
| EP0885179A1 (fr) | Procede de production de composes aromatiques fluores et de composes heteroaromatiques fluores renfermant de l'azote | |
| EP0024612A2 (fr) | Ethers 4-fluoro-3-phénoxy benzyliques, procédé pour leur préparation et leur utilisation | |
| EP0012942B1 (fr) | Procédé de préparation électrolytique de benzaldéhydes | |
| EP0287954B1 (fr) | Acétals dialkyls de benzaldéhyde, leur préparation et leur utilisation | |
| EP0047948B1 (fr) | Procédé pour la préparation de composés carbonyle polyfluorés et quelques représentants de cette famille de composés | |
| DE19526464C1 (de) | Chirale tertiäre Phosphine und Verfahren zu ihrer Herstellung | |
| DD244552A5 (de) | Verfahren zur herstellung von azetidin-derivaten | |
| EP0243607B1 (fr) | Procédé de préparation de bicarbamates | |
| DE4327361A1 (de) | Verfahren zur Herstellung von Benzaldehyddialkylacetalen | |
| DE3152459C2 (fr) | ||
| DE68906589T2 (de) | Elektrochemische Synthese von 2-Aryl-Hydrochinonen. | |
| EP0047945A2 (fr) | Procédé pour la préparation de fluorures d'acides perfluoro-carbonylsulfoniques et halogénures d'acides de fluorosulfate perfluoro-alcanesulfoniques obtenus comme intermédiaires dans ce procédé | |
| DE2428878C2 (de) | Verfahren zur Herstellung von p-Hydroxymethyl-benzoesäureestern | |
| EP0179377B1 (fr) | Procédé pour la préparation d'alkoxy-1 isochromanes et alkoxy-1 alkylisochromanes | |
| DE2331711A1 (de) | Verfahren zur selektiven elektrolytischen entbromierung | |
| DE4407986A1 (de) | Verfahren zur Herstellung von o-Phthalaldehydtetraalkylacetalen | |
| EP0711851B1 (fr) | Procédé de production de p-Hydroxybenzaldéhydes | |
| EP0237769B1 (fr) | Acétals dialkyliques de benzaldéhyde | |
| EP0347690A2 (fr) | Procédé de préparation de dérivés du benzène et dérivés du benzène | |
| DE2547464A1 (de) | Verfahren zur herstellung von hydrochinondimethylaethern | |
| DE102005036687A1 (de) | Verfahren zur Herstellung von 1,1,4,4,-Tetraalkoxy-but-2-enderivaten | |
| EP0621352A2 (fr) | Procédé de préparation de tétraalkylacétals de téréphtalaldéhyde | |
| DE2306919A1 (de) | Verfahren zur herstellung von aminochlor-benzaldehyden |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): CH DE FR GB LI |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CLARIANT GMBH |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE CH DE FR GB IT LI NL |
|
| 17P | Request for examination filed |
Effective date: 19981029 |
|
| 17Q | First examination report despatched |
Effective date: 19990604 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| RBV | Designated contracting states (corrected) |
Designated state(s): CH DE FR GB LI |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE FR GB LI |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REF | Corresponds to: |
Ref document number: 59605791 Country of ref document: DE Date of ref document: 20000928 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20001025 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20031015 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20031017 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20031020 Year of fee payment: 8 Ref country code: FR Payment date: 20031020 Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041210 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041231 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050701 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20041210 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050831 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |